CS196265B2 - Catalyst for ethylene polymerisation - Google Patents

Description

The invention relates to a catalyst system for the polymerization of ethylene consisting of alkyl halides, alkyl derivatives or metal hydrides of the first three groups of the periodic system and a reaction product of titanium tetrachloride and a carbonyl compound of manganese. The reaction product of the titanium tetrachloride and the carbonyl compound of manganese can be used as such or can be finely dispersed on a material with a high specific surface area.

It is known that catalytically active titanium halides are generally used in the low pressure polymerization of α-olefins and are prepared by the reduction of titanium halides with alkylaluminium or alkyl halides. The reaction is generally carried out under an inert atmosphere and in the presence of an inert solvent. The catalyst thus prepared is then used together with the alkyl metal compounds to polymerize α-olefins in an organic solvent suspension at low monomer pressures.

However, these titanium halides are contaminated with aluminum compounds and do not exhibit too high catalytic activity, so that the final polymer requires expensive washing operations to remove catalyst residues.

Recently, a method was proposed, according to ·

which are obtained by polymerization catalysts with improved efficiency by applying titanium halides to inorganic substances.

as carriers, for example, magnesium oxide, magnesium chloride, silica or alumina were used; all of these carriers have a high specific surface area, but it should be noted that the catalytic activity of the titanium compounds on the above-mentioned materials as catalytic carriers is highly dependent on the chemical nature of their surface, so that these carriers often have to undergo treatment with Grignard derivatives, or hydrogen to improve their own efficacy.

The present invention provides a high activity catalyst which requires no pretreatment when used on a support.

This catalyst also consists of an alkyl halide, alkyl derivative or metal hydride belonging to the first three groups of the Periodic Table of Elements, bj a transition metal component consisting of the reaction product of titanium tetrachloride and the carbonyl manganese compound of formula MnaCO10 or Mn (.CO) 5Cl. .

It is preferred that the transition component

The metal is impregnated in a carrier selected from metal halides of the first or second group of the Periodic Table of the Elements, the amount of manganese being 0.1 to 10, preferably up to 3% by weight, based on the carrier.

In any case, the polymerization activity of the catalyst of the invention is higher than that of catalysts containing only titanium tetrachloride supported. The catalysts of the present invention have a favorable hydrogen behavior and provide ethylene polymers with a narrow molecular weight range. .

The following examples serve to illustrate the invention without limiting it in any way. The following operating conditions ("standard polymerization") are used: The solvent, the organometallic compound (in a concentration of 0.2% by volume) and the above-described reaction product of the transition metals are introduced into an autoclave thermostatized at 85 ° C. The ethylene pressure was kept constant throughout the experiment, which was 6 hours. The obtained polymers are dried under vacuum to constant weight before calculating the yield. The symbol MF denotes a melt flow index of g / 10 min.

Example 1 g NaCl, finely ground and oven dried at 400 ° C, was refluxed in TICH (50 cc) together with Mn 2 (CO) 10 (0.5 g) for 6 hours. The product was filtered, washed with ligroin and dried under vacuum. The product had the following composition:

Ti = 1.83%

Mn = 1.10%

When using 200 mg of this product in standard polymerization at a polymerization time of 6 hours at P _H / P _CH = 1/1 (MPa / MPa)

In order to _produce 278 g of a polymer with MF ₂₁ = _16.800 , MF ₂₁ , ₆ = 30.784, MF ₂₁ , ₆ / MF ₂ , ₁₆ = 38.48 and containing 13.2 ppm Ti or 21.5 ppm Ti + Mn. .

Example 2

16.8 g of NaCl, finely ground (same as in Example 1), was refluxed in TiCl4 (50 ml) together with MnzfCO3 (0.5 g) for 4 hours.

The product was filtered, washed repeatedly with hexane and dried. It had the following composition:

TI = 0.97%

Mn = 0.49 Ψο

245 mg of this product was used in the polymerization test for 2 hours at relative pressures of H 2 and C 2 H 4 equal to 0.8 / 1.2 MPa / MPa.

65 g of a polymer with MF ₂ , ₁₆ = 0.263, MFzu = 8.47, MF ₂₁ , ₆ / MF _{2> 16} = 32.2 and containing 36.5 ppm Ti or 55 ppm Ti + Mn were obtained.

Example 3

KCl, finely ground and dried at 400 ° C (5 grams) was suspended in TiCl 2 and refluxed for 4 hours with Mn 2 (CO) 10 (0.18 g).

The product was filtered, washed with hexane and dried under vacuum. The product had the following composition:

Ti = 2.29%

Mn = 0.68%

158 mg of this product was used in polymerization for 6 hours at H2 / C2H4 relative pressures equal to 0.8 / 1.2 MPa / MPa. 466 g of a polymer with MF ₂ , ₁₆ = 0.331, MF - 11.55, MF _{21 were obtained} . ₆ / MF ₂ , ₁₆ = 348, and containing 7.77 ppm Ti and 10.35 ppm Ti + Mn. Example 4

MgCl 2 (10 g) previously dried under a stream of HCl at 350 ° C was refluxed with stirring. in 50 ml of TiCl4 together with Mn2 (CO) 10 (0.45 g) for 6 hours. After the processing of the catalyst described above, the catalyst had the following composition:

Ti = 0.90%

Mn = 0.54%

By using 290 mg of this product by polymerization for 2 hours at a P _H / PC ^r0 ^ · h 2 4 2 No 1 / 0.5 (psi / MPa) was 53 g of polymer produced with the MF _{2> 16} ~ 2.96, MF ₂ and ₆ = 110.6, MF ₂ and ₅ / / MF _2j i ₆ = 37.2 and containing 49.2 ppm of Ti or 78.6 ppm of Mn + Ti.

Example 5

5.9 g of KCl, finely ground and dried, were refluxed with 0.53 g of Mn (GO) sCl and 30 cm ^{3 of} TiCl 4 for 6 hours.

The product was filtered, washed with ligroin and dried under vacuum. It had the following composition: Ti = 2.80%

Mn = 1.40%

Using 305 mg of this product in polymerization for 2 hours at a pressure ratio P _h / Pch = 1 / 0.5 (MPa / MPa), 2 4 heno 190 g of polymer with MF ₂ , ₁₆ = 8.29, MF were produced. ₂ and ₆ = 300.46, MF _{21 6} / MF _2i16 = 36.24, and containing 45 ppm Ti and 67 ppm Ti + Mn.

EXAMPLE 1 a d

Mn (CO) 5Cl was prepared by passing a weak chlorine stream through a solution of Mti2 (CO) 10 v

6.5

CCl 4 at 0 ° C, evaporation of the volatiles under vacuum and sublimation at 40 ° C and 13.3 Pa [Abel and Milkinson - J. Chem. Soc. 1501, (195a)]. The desired product containing 15.37% chlorine was obtained

15.21% of the theoretical value.

The product obtained was reacted with an excess of TiCl 3 and kept boiling until gas evolution ceased (about 16 hours).

A violet solid product was obtained, which was filtered, washed with ligroin to remove excess TiCl 4, dried under vacuum and showed the following elemental analysis:

theory for TiCl 3 found and MnCl 2

TI% 19.25 17.11

Mn% 20.20 19.60

Cl% 60.20 63.27

The product so obtained was used for the polymerization of ethylene according to the conditions referred to as "standard polymerization". The results are shown in the following table:

Catalytic system MnTiCls (unsupported) - Al (i But) 3

íWžrs' aš and + • · in '' M CO CO 05 CO-ZO ^: · '· ts CO' Φ C \ 3,. . , ·. ·. ·. . rl H ' íc ftH and· CD CO Tt * O OO i · · · · · · · · · CO H CM CD CO yield (G) ino eo irt CO D3 H ΙΓ3 IS R H rl Ό TH iSÍ te _t tn oa co 'ce eo iT nrf te 2 \O what what in N fa with What cq ^ TT ^ σ> _Λ of Γ r CO CO * uf three in what Ή rd * eí En with CO Cs CO © CON Ί Ί N 0Ί TO) CM CM CM CM Γ ** te OS te Si 'ζ'Ν <0 and te te _s inin sxřn O O o o ' ID no what about o 'o o o' ř- < O 53 N Č? W CD. Θ 53 G 44 ιη ιη ττ co O co co 00 co n rl rlHN Example, CO b · 00 05 O τ— |

Claims (2)

Catalyst for the polymerization of ethylene, characterized in that it consists of an alkyl halide, an alkyl derivative or a metal hydride belonging to the first three groups of the Periodic Table of the Elements and a transition metal component consisting of a reaction product of titanium tetrachloride and a carbonyl manganese compound of the formula Y N E L u u Mn (CO) sCl optionally impregnated with the support. Catalyst according to claim 1, characterized in that the transition metal component is impregnated in a carrier selected from metal halides of the first or second group of the periodic system, the amount of manganese being 0.1 to 10, preferably 1 to 3% by weight. relative to the carrier.